Research Article, Issue 3
Analytical Methods in Environmental Chemistry Journal
Journal home page: www.amecj.com/ir
AMECJ
------------------------
Maling Goua,b and Baharak Bahrami Yarahmadic,*
a State Key Laboratory of Biotherapy and Cancer Center, West China Hospital, Sichuan University and Collaborative Innovation Center for Biotherapy, Chengdu
610041, China
b Department of Thoracic Oncology, Cancer Center, West China Hospital, Medical School, Sichuan University, Chengdu 610041, China
c,* Occupational Health Engineering Department, School of Public Health, Kerman University of Medical Sciences, Kerman, Iran
cardiovascular, CNS, Liver, renal, and others, may
be lead to dangers acute and chronic disease such as,
cancer and multiple sclerosis [2-5]. So heavy metals
enter to human body and cause many problem with
adverse health effects [6]. Heavy metals have a
normal range in environment (air, soil, water), but
industrial activity increase their concentrations
in the environment matrix and humans [7]. The
Pb(II) was widely used in industrial processes
and has highly toxic effect in humans as a major
environmental pollutant [8]. In battery factory, the
lead exposure is still the main subject in the human
workplace and occupational health but some
Separation and determination of lead in human urine and water samples
based on thiol functionalized mesoporous silica nanoparticles packed
on cartridges by micro column fast micro solid-phase extraction
1. Introduction
Heavy metals such as; arsenic (As), lead
(Pb), Cobalt (Co), chromium (Cr) and mercury
(Hg) and nickel (Ni) with densities about 5 gram per
cubic centimeter are called heavy metals. Natural
and human sources of heavy metals are mineral
resources development, metal processing and
smelting, petrochemical company, factory
emissions, and sewage irrigation [1]. Exposure to
heavy metals especially mercury caused to different
disease in humans. For example, disorders of the
Corresponding Author: Baharak Bahrami Yarahmadi,
Email: baharakb72@gmail.com
https://doi.org/10.24200/amecj.v2.i03.72
A R T I C L E I N F O:
Received 3 Jul 2019
Revised form 24 Aug 2019
Accepted 5 Sep 2019
Available online 20 Sep 2019
Keywords:
Lead, Human sample,
Thiol-mesoporous silica
nanoparticles,
Packed column micro solid phase
extraction,
Electrothermal atomic absorption
spectrometry
A B S T R A C T
An efficient method based on thiol functionalized mesoporous
silica nanoparticles (HS-MSNPs) was used for extraction of lead
ions (PbII) from urine and water samples by packed column
micro solid phase extraction (PC-MSPE). By procedure, 15 mg of
HS-MSNPs packed in syringe cartridges (SC, 5mL) with cellulose
membrane and pH adjusting at 5.5-6.5. Then, the lead of urine and
water sample was efficiently extracted on HS-MSNPs after pushing
the plunger of a syringe. Finally, the Pb (II) was back-extracted
with inorganic acid solution and the remained solution determined
by electrothermal atomic absorption spectrometry (ET-AAS). By
optimization conditions, the enrichment factor, LOD, linear range
and RSD% was obtained 24.8, 0.04 μg L-1, 0.12-5.5 μg L-1 and less
than 5%, respectively for 5 mL of urine samples. The validation was
confirmed by spiking of real samples and using certified reference
material (CRM, NIST) in water and urine sample.
Lead extraction by PC-MSPE technique Maling Gou et al
Analytical Methods in Environmental Chemistry Journal Vol 2 (2019) 39-50
40 Analytical Methods in Environmental Chemistry Journal; Vol. 3 (2019)
protective instruments used to reduce the emission
of lead [9-11]. Lead is used for pipe, instruments
and medical device as a resistant to corrosion and
X-ray. The lead with melting point of 327 °C and
evaporation pressure out 1.77 mmHg was used
in industrial process with different application
such as, battery, ceramic, balls, rubber, crystals,
and pesticide [12]. The international agency for
research on cancer (IARC) reported, the inorganic
and organic lead caused to carcinogenic effect in
humans [7, 12, 13]. Also, the half-life of Pb in blood,
soft tissue and bone was obtained about 35 days,
50 days and 20 years, respectively [6, 14, 15]. The
previously papers showed that, the lead poisoning
has adverse health effects in human systems and
acute and chronic exposure caused to disorder in
cardiovascular, digestive, and nervous systems
[12]. Car exhausts, contaminated food, industrial
emission, and air and soil pollution could be a
good example of lead exposure by skin, inhalation
or ingestion. Symptoms of lead toxicity included,
abdominal pain, anorexia, tremor, CNS problem,
MS, constipation, myalgia, irritability, and anemia.
Lead poisoning can be caused an acute abdominal
pain [16, 17]. The toxicity of lead evaluates in the
blood, hair, urine, and stool samples by ET-AAS
or ICP instruments. Lead can be excreted in urine
by the renal, so, nephrotoxicity was occurred in
both acute and chronic exposure of lead in adults
and children’s. The nephrotoxic effects of lead
has been observing at high blood concentrations
1.93 -2.42 μmol L-1 (40-50 μg dL-1) [15, 18]. The
various methods was used for determination lead
in different matrix samples [13, 19]. The most
well-known methods are; flame atomic absorption
spectrometry (FAAS) [20], graphite furnace atomic
absorption spectrometry (GFAAS) [21], inductively
coupled plasma-optical emission spectrometry
(ICP-OES) [13], and inductively coupled plasma-
mass spectrometry (ICP-MS) [22]. Due to the
low concentration of lead in biological matrix,
interferences ions and difficulty analysis of lead,
a sample preparation step before the determination
process is necessary [23, 24]. Liquid-liquid
extraction/micro extraction(LLE/LLME) [25], co-
precipitation [26], cloud point extraction(CPE)
[27], and solid-phase extraction/micro solid-phase
extraction (SPE&MSPE) [28] are the most effective
pre-concentration procedures. Also, different
sorbets were evaluated for SPE methods. Recently,
nanosorbents as favorite sorbent was considered
for extraction heavy metals in water and human
samples [29]. As reliable analytical performance
for metal adsorption /determination, a variety of
nanomaterials include; modified macromolecules
[28], carbon nanotubes [30], magnetic materials
[31], mesoporous materials [32], and ion-imprinted
polymers [33], ferric oxide [34], titanium oxide
[35], manganese oxide [36], and aluminum oxide
[37] have been used in SPE. Nanomaterials with
high surface area, high adsorption, usability, good
recovery, low time extraction are candidate for
SPE analytical approach[13]. Some advantages
such as high sensitivity, low sample requirement,
low solvent consumption, simplicity, and easy
automation, Solid-phase micro extraction (SPME)
as successful technique has been used for extraction
metals from liquid phase [38]. Other nanomaterials
include; polymer nanoparticles, nanocarbon,
nanozeolites, functionalized nanomaterials and
mesoporous silica nanoparticles was used as
efficient sorbent for extraction heavy metals by
SPE or MSPE [39]. Due to excellent dispensability
and high adsorption capacity with large specific
surface area, mesoporous silica based on monolithic
column have attracted by SPE/SPME procedure
[40]. For analyzing heavy metals based on SPE
method, various functionalized mesoporous silica
with thiol, amine, phosphonate, etc. have been used.
Recently, the syringe-based SPE device containing
thiol and amine functionalized mesoporous silica
was used for the simultaneous uptake of As(III) and
As(V) in liquid samples [38, 40]. In this work, lead
in urine and waters were extracted based on HS-
MSNPs by PC-MSPE technique before determined
by ET-AAS. By proposed method, HS-MSNPs as
an adsorbent were validated by CRM. The thiol
functionalized MSNPs was used as complexing
agent for extraction of lead from samples. The
chemical bonding of HS-MSNPs was occurred
41
Lead extraction by PC-MSPE technique Maling Gou et al
based on the thiol-lead bonding by sorbent in liquid
phase.
2. Material and method
2.1. Apparatus and Reagents
The ultra-pure reagents such as, sodium
hydroxide (NaOH), hydrogen peroxide (H2O2),
inorganic and organic acids( H2SO4, HNO3, HCl,
CH3COOH), T-ethoxysilane (TEOS, CAS N:
800-6580025), Triethanolamine hydrochloride
(TEAH3, HOCH2CH2)3N , HCl, CAS N: 102-
71-6), hexadecyltrimethylammonium bromide
as ammonium surfactant; (CTAB, C19H42BrN ,
N: 57-09-0), sodium hydroxide, lead nitrate salt
(CAS number: 10099-74-8) and - 3-Triethoxysilyl-
1-propanethiol (C9H22SO3Si, CAS N: 14814-
09-6) was purchased from Sigma Aldrich
(Darmstadt,Germany). Sodium silicate solution
(Na2O(SiO2)x · xH2O , N: 338443, Sigma Germany),
pure ethanol solution and acetone were prepared
from Merck(Germany). The standard solution of
Pb(II) was prepared from the lead chloride [liquid
of Pb Cl2] as 1 g L-1 solution in HCl 1%. The micro
gram concentrations of Pb Cl2 were prepared
daily by dilution HCl. For evaluation of the purity
of HS─ MSNPs, toxic metals such mercury; lead
determined by ET-AAS. The pH of samples was
adjusted by buffer solutions. The CH3COONa/
CH3COOH and ammonium buffer solutions were
selected for pH of 3-7and 7.5-10. The results were
obtained by electrothermal atomic absorption
spectrometer (GBC, ET-AAS, Australia). A
deuterium background correction lamp (UV) and
hollow cathode lamp with 5 mA and a wavelength
of 283.3 nm was adjusted. The pH of samples was
determined by pH meter of Metrohm, Germany.
2.2. Synthesis of thiol functionalized MSNPs
In a typical synthesis, tri-ethoxysilane was added
to predetermine amounts of Triethanolamine
hydrochloride. The solution was heated up to 140
°C under vigorous stirring. After cooling down to
90 °C, CTAB was added to this solution. The final
molar compositions of the reactants were 1.0 TEOS:
3.5 TEAH3: 0.25 CTAB: 90 H2O [41-43]. For thiol
functionalization of calcined MSNPs, 1.4 g of 3-
mercaptopropyltriethoxysilane (C9H22SO3Si) and
1.5 g of calcined MSNPs in presence of toluene,
were refluxed for 24 h and then washed with DW.
The obtained thiol functionalized MSNPs (HS-
MSNPs was dried at 75oC.
2.3. Characterization
The scanning electron microscopy (SEM) and
transmission electron microscopy (TEM) was
used for morphology and size morphology of the
HS-MSNPs by Philips Co., Netherland (model
PW3710 & model CM30) (Fig. 1a and b). The
elemental analyzer was used for determination
of elemental composition ratio H/C, N/C, S/C or
C/N (GBC, AUS). X-ray diffraction (XRD) peak
of HS-MSNPs and MSNPs were obtained with
by wavelength 0.15 nm (Fig. 2) (Seifert TT 3000,
Germany). Functional groups of SH on MSNPs
Fig. 1. (a)SEM of HS-MSNPs and (b) TEM of HS-MSNPs
42 Analytical Methods in Environmental Chemistry Journal; Vol. 3 (2019)
as HS-MSNPs material were analyzed by FTIR
in Waveland between 300 cm−1 to 4000 cm−1 (Fig.
3). The HS band was showed in Waveland of 2500
cm−1 (Germany).
2.4. General procedure
The packed column micro solid phase extraction
(PC-MSPE) was used for separation and
preconcentration of Pb(II) ions in human urine,
standard solution and water samples. First, 5 mL
of the lead standard solution containing 0.1 -5.5
μg L−1 as a LLOQ and ULOQ was used and pH
adjusted up to 6. After optimized pH, the standard
and urine samples directly transferred to in 5 mL
of syringe cartridges with cellulose membrane
which was already packed with 15 mg of HS-
MSNPs and MSNPs as a sandwich form between
membranes manually. The syringe cartridges (SC)
included packed sorbent in cellulose membrane
(PSCM) was used for extraction of Pb (II) from
Fig. 2. The XRD of HS-MSNPs
Fig. 3. FT-IR spectra patterns HS-MSNPs in 2500 cm−1
43
Lead extraction by PC-MSPE technique Maling Gou et al
liquid phase by PC-MSPE. Then the urine
samples were fast extracted through PSCM of
HS-MSNPs with pushing the plunger and the
solid/liquid phases were separated. The Pb ions
chemically and physically absorbed on HS-
MSNPs. Finally, Pb(II) ions retained on the
HS-MSNPs were eluted by passing 0.2 mL of
nitric acid (0.3 M) through the SC and the lead
value in the eluent was determined by ET-AAS
(Fig. 4). The project approved by the ethical
committee of K.U.M.S. (Ethical
Code:IR.KMU.REC. 1398. 453)
3. Results and Discussion
3.1. The pH optimization
The pH is one of the most important parameters
which were affected on lead extraction by PC-
MSPE procedure. The effect of urine and standard
pH on the extraction of Pb (II) by HS-MSNPs
and MSNPs has investigated from pH of 1-12
containing 0.1-5.5 µg L-1 of lead ions by PC-MSPE
method. Also, the extraction Pb ions in human
urine sample were investigated in human pH. The
results showed us, the extraction efficiencies of Pb
(II) in urine samples were increased in pH from 5.5
to 6.5. The maximum recoveries were achieved in
optimized pH (more than 97%) and decreased in
5.5 > pH > 6.5. So, the pH of 6.0 was selected as
optimized pH for Pb extraction in urine and water
samples. Furthermore, the Pb(II) and other metals
was more extracted by extra mass (50 mg) of HS-
MSNPs as physically adsorption simultaneity. In
optimized conditions, the mean extraction of Pb
was obtained less than 98.7% and 34.6% by 15
mg of HS-MSNPs and MSNPs, respectively at
pH=6. The extraction mechanism of Pb ions on
the HS-MSNPs is mainly based on the electrostatic
attractions of deprotonated sulfur of thiol groups
with the positively charged Pb ions.
3.2. The mass optimization
For optimization of proposed method, the amounts
(mg) of HS-MSNPs and MSNPs in the range of 1
to 30 mg were studied for extraction of 0.1-5.5 µg
L-1 of Pb(II) in human urine and water samples.
The results showed us, more than 12.5 mg of HS-
MSNPs had good extraction recovery for Pb(II)
in standard samples. So, 15 mg of HS-MSNPs
was used as optimized amount of HS-MSNPs by
PC-MSPE method (Fig. 6). More than 15 mg of
HS-MSNPs got no significant extraction on the
recovery of lead urine and water samples. For
15 mg of MSNPs, the extraction recovery was
obtained less than 35% at pH=6 and was increased
up to 44.4 % at pH=3.
3. 3. The sample volume optimization
The sample volume effected on the recovery of
Pb(II) ions based on PC-MSPE in standard and
human urine samples. So, the sample volume was
evaluated from 1-20 mL in optimized conditions.
Fig. 4. The general procedure for lead extraction by PC-MSPE
44 Analytical Methods in Environmental Chemistry Journal; Vol. 3 (2019)
The results showed us, the quantitative extraction
was achieved less than 5 mL sample by 0.1 – 2.5 µg
L−1 of Pb as LLOQ and ULOQ range (≈97%). The
extraction recovery was reduced more than 8 m and
10 mL of sample volume for urine and standard/
water samples, respectively. As normal range of
Pb in urine and waters (TLVs) a syringe cartridges
(SC) of 5 mL were used for urine and water samples
(Fig. 7).
3. 4. Adsorption capacity and separation time
In the batch system, the adsorption capacity (AC)
of HS-MSNPs and MSNPs for lead extraction was
calculated by ET-AAS. The adsorption capacity of
Pb (II) was investigated for 5 mL of human urine
sample and standard solution at pH=6 (15 mg
HS-MSNPs and MSNPs). The pH was adjusted
by using buffer solution and after shaking of SC,
lead ions chemically and physically absorbed on
sorbents. The residual solutions were determined
Fig. 5. The effect of pH on lead extraction by HS-MSNPs and MSNPs
Fig. 6. The effect of mass of HS-MSNP on lead extraction by PC-MSPE method
45
Lead extraction by PC-MSPE technique Maling Gou et al
by ET-AAS. The adsorption capacity of HS-MSNPs
and MSNPs for Pb ions was 186.3 mg g-1 and
64.8 mg g-1, respectively. The results showed, the
recovery of HS-MSNPs was higher than MSNPs
as characterization and chemical bonding. So, the
HS-MSNPs were used as excellent sorbent for
extraction of Pb (II) in this study. Also separation
time for extraction of lead ions was investigated
between 2 min to 10 min. The result showed
that, 4.5 min was an optimum time for excellent
recovery. This time was controlled by pushing the
plunger.
3. 5. Back extraction process
The maximum recovery for lead extraction was
carried out in optimum conditions. The lead was
back extracted from HS-MSNPs by different
concentration of inorganic and organic acids
such as HNO3, HCl, CH3COOH and H2SO4. The
chemical adsorption between HS-MSNPs and Pb
ions was dissociated at acidic pH. For optimizing,
0.1-0.5 mL of acids with different concentration
from 0.1- 0.5 mol L-1 was studied. Based on results,
0.2 mL of HNO3 (0.3 mol L-1) had good recovery
(Fig. 8).
3. 6. Interference study
By PC-MSPE method, the interference of coexisting
ions (cations and anions)such as; SO4
2-, Cl-, Br-,
NO3
-, CO3
2-, Cd2+, AS3+, Hg2+, Ag+, Co2+, CU 2+,
Zn2+,Mn2+, V3+, Al3+ and Ni2+ in water and urine
samples was studied. So, different concentration of
coexisting ions (1─5 mg L-1) was added to 5 mL of
standard sample solution with lead concentration of
5.5 μg L-1. Based on results, the most concomitant
ions cannot effect on extraction of Pb in samples.
The mean of concentration ratio of above coexisting
ions per lead was less than 500. Therefore, the Pb
ions in urine samples were efficiently extracted
with HS-MSNPs in present of coexisting ions (less
than 5%).
3.7. Discussion
Mortada et al investigated the pre-concentration of
Pb2+ from blood and urine samples with mesoporous
strontium titanate nanoparticles and determined
the samples by FAAS. The characterization was
obtained by FT-IR, XRD, SEM-EDX, and TEM.
In optimized conditions, the pH, shaking time,
mass sorbent and adsorption capacity was achieved
at 6, 20 min, 50 mg and 155.6 mg g−1 which was
lower than PC-MSPE procedure in this study. The
limit of detection and relative standard deviation
was 1.75 μg L−1 and 2.5%, respectively which was
higher than our proposed method by HS-MSNPs
(LOD=0.04 μg L-1, 2.2 %)[44]. In another research,
Fig. 7. The effect sample volume on lead extraction in water and urine samples
46 Analytical Methods in Environmental Chemistry Journal; Vol. 3 (2019)
Behbahani et al used the method of solvent-assisted
dispersive solid-phase extraction (SA-DSPE) to
determine lead in fruit and water samples. After
lead extraction the samples was determined by
flame atomic absorption spectrophotometer
(F-AAS). Based on results, LOD =1.2 μg L−1 was
obtained as compared to lower LOD (0.04 μg
L-1) by PC-MSPE method [45]. Kakavandi et
al, reported ultrasonic assisted-dispersive solid-
phase extraction based on ion-imprinted polymer
(UA-DSPE-IIP) nanoparticles as a selective
extraction for lead ions. Box-Behnken design
(BBD) was used for the optimization of sorption
and desorption steps in UA-DSPE-IIP. Under the
optimized conditions, the limit of detection and
relative standard deviation for the detection of
lead ions by UA-DSPE-IIP was found to be 0.7
μg L−1 and <4%, respectively which was higher
than proposed method based on HS-MSNPs by
PC-MSPE method [46]. Also, a magnetic sorbent
(MoS2-Fe3O4) based on dispersive solid-phase
microextraction (DSPME) was used for separation
Pb(II) and copper(II) ions from water samples by
Soylak. LODs and RSD of 3.3 μg·L−1, 4.9 for Pb(II)
and of 1.8 μg·L−1, 1.5% for Cu(II), was achieved
by F-AAS. So, PC-MSPE method had better results
as compared to MoS2-Fe3O4 sorbent [47]. Jiamei
at al showed mesoporous silica-grafted graphene
oxide (GO-SBA-15) as sorbent and packed it in
an SPE microcolumn with solution-cathode glow
discharge-atomic emission spectrometry (SCGD-
AES) method. The detection limit (DL) of Pb(II)
was calculated to be 0.91 μg L− 1 which was
higher than PC-MSPE procedure [48]. Shahad
et al used mesoporous silica with nanospheres
as a substrate and the organic ligand of 2,5-di
mercapto-1,3,4-thiadiazole, for lead removal from
wastewater with LOD of 0.48 µg L-1 and adsorption
capacity of 67.20 mg g-1[49]. sobhi et al suggested
ultrasonic-assisted dispersive micro-solid phase
extraction (d-μSPE) method with GF-AAS for
measuring of lead in water and urine samples by
silica-based amino-tagged nano sorbent (MCM-
41@NH2. The result showed that linear range,
RSD and recovery was obtained 0.1–1.0 μg L-1,
4.8–9.2% and 92–110%, respectively. The wide
linear range and lower RSD was achieved for PC-
MSPE as compared to d-μSPE method [50]. Amiri
et al synthesized magnetic natural clinoptilolite
(CP for simultaneous determination of lead (II)
and cadmium (II) ions by FAAS. The limit of
detection (LOD) using this method were found to
be 0.93[51]. Raoof et al use the graphene oxide-
soluble eggshell membrane protein (GO-SEP)
Fig. 8. The effect acids on lead extraction with HS-MSNPs
47
Lead extraction by PC-MSPE technique Maling Gou et al
by inductively coupled plasma-optical emission
spectrometry (ICP-OES). The GO-SEP-ICP-OES
with LOD of 0.1 µg.L−1 was equal to PC-MSPE
method [52]. Baile et al used magnetic dispersive
solid-phase microextraction (MDSPME) method,
based on ZSM-5 zeolite decorated with iron oxide
magnetic nanoparticles (i.e., ZSM-5/Fe2O3) for
the simultaneous separation and preconcentration
of cadmium (Cd), mercury (Hg) and lead (Pb) from
urine [53].
3.8. Validation of procedure
A novel method based on HS-MSNPs was
applied for lead extraction for 5 mL of urine and
water samples by PC-MSPE. For validation, real
samples (water and urine) were spiked by standard
lead samples in different concentration from LLOQ
to ULOQ. The method was approved with good
precision and accuracy results with low RSD%
(Table 1). Also, the proposed method was validated
by power instrumental analysis (ICP-MS) as
compared to PC-MSPE procedure (Table 2). The
certified reference material (CRM, NIST) in water
and wastewater samples were used for validating
of results by PC-MSPE method. Experimental
results of the CRM sample were satisfactorily
confirmed the certified values of lead (Table 3).
The recoveries of spiked water and urine samples
Table 2. Comparing of PC-MSPE method with ICPMS for lead determination
Sample Added ICP-MS PC-MSPE
ICP-MS
Recovery%
PC-MSPE
Recovery%
Urine ------ 1.82 ± 0.04 1.78 ± 0.09 ------ ------
2.0 3.79 ± 0.05 3.69 ± 0.21 98.5 95.5
Water ------ 0.73 ± 0.02 0..68 ± 0.03 ------ ------
0.5 1.21± 0.03 1.19 ± 0.05 96.0 102.0
* Mean of three determinations ± confidence interval (P = 0.95, n =10).
Table 3. Validation methodology by Sigma CRM and ICP-MS for PC-MSPE method
CRM sample ICP-MS CRM (μg/L) *Found(μg L-1) Recovery%
*ERMCA713 4.92 ± 0.12 4.97 ± 0.17 4.88 ± 2.4 98.2
1640a 1.19 ± 0.02 1.21 ± 0.02 1.23± 0.06 101.6
Urine 2.07 ± 0.09 ------ 1.98 ± 0.09 95.6
Drinking water 0.51± 0.01 ------ 0.49± 0.03 96.2
*Mean of three determinations ± confidence interval (P = 0.95, n =10)
a Sigma Aldrich, Cat. No. ERMCA713, lead in wastewater diluted up to 10.
b NIST SRM 1640a, lead in water, diluted up to 10.
Table 1. Validation of PC-MSPE method based on spike of lead standard concentration
Sample Added (μg L-1) *Found(μg L-1) Recovery%
Urine A ------ 2.34 ± 0.09 ------
2.0 4.28 ± 0.17 97
Urine B ------ 1.02± 0.04 ------
1.0 1.97± 0.11 95
Well Water ------ 0.46 ± 0.02 ------
0.5 0.97± 0.05 102
a Wastewater ------ 2.16 ± 0.12 ------
2.0 4.14± 0.18 99
*Mean of three determinations ± confidence interval (P = 0.95, n =10).
a Wastewater samples was diluted with DW (1:20)
48 Analytical Methods in Environmental Chemistry Journal; Vol. 3 (2019)
for Pb(II) were ranged from 95% to 102%, which
demonstrated that the PC-MSPE method was
satisfactory extracted and determined Pb ions in
human urine samples (n=10).
4. Conclusions
The simple, applied and reliable SPE technique for
determination of trace levels of Pb (II) ions in real
water and urine samples was developed based on
HS-MSNPs by ET-AAS. The PC-MSPE method
provided good recoveries (>95%) in optimized
conditions. By procedure, reproducibility and
reliability data with low RSD (under 5%) in 10
experiments were obtained. The batch adsorption
capacities of lead on MSNPs and HS-MSNPs were
found to be 64.8 and 186.3 mg g−1, respectively.
The PC-MSPE procedure has some advantages
such as, excellent separation, high surface area, low
consumption of only 15 mg of HS-MSNPs, good
enrichment factor for 5 mL of sample, only 0.2 mL
of eluent per extraction, high absorption capacities,
low LOD, and favorite reusability (more than 20).
It is expected that the PC-MSPE procedure based
on nanotechnology could successfully be extracted
lead ions from urine and water samples.
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